Professional Documents
Culture Documents
CTRL PDF
CTRL PDF
ca
NRCC-47711
Masson, J-F.
The material in this document is covered by the provisions of the Copyright Act, by Canadian laws, policies, regulations and international
agreements. Such provisions serve to identify the information source and, in specific instances, to prohibit reproduction of materials without
written permission. For more information visit http://laws.justice.gc.ca/en/showtdm/cs/C-42
Les renseignements dans ce document sont protgs par la Loi sur le droit d'auteur, par les lois, les politiques et les rglements du Canada et
des accords internationaux. Ces dispositions permettent d'identifier la source de l'information et, dans certains cas, d'interdire la copie de
documents sans permission crite. Pour obtenir de plus amples renseignements : http://lois.justice.gc.ca/fr/showtdm/cs/C-42
1
J-F Masson
Institute for Research in Construction,
National Research Council of Canada, Ottawa, Ontario, Canada, K1A 0R6
Phone: 613-993-2144. Fax: 613-952-8102. E-mail: jean-franois.masson@nrc.gc.ca
Abstract
Bitumen finds great use in paving and roofing applications. To enhance or extend its
PPA is a reactive oligomer, a short chain polymer, whose reaction with bitumen is poorly
of PPA and bitumen are reviewed. It is concluded that PPA cannot dissociate and react
Introduction
Bitumen is used in over two hundred applications, most of which relate to civil
engineering, and to paving and roofing in particular (1). In an attempt to change its
characteristics and improve its performance, bitumen is often modified with an elastomer
(2, 3), a plastomer (4, 5, 6, 7), a thermoset (8, 9), sulphur (10, 11), or a mineral acid
(12). There is now much interest in the use of polyphosphoric acid (PPA) to modify
It is common for material formulators and developers to use bitumens of different sources
as dictated by market forces. As bitumen changes, it is often difficult to predict the effect
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
2
high temperatures. In some cases, the modifier reacts with bitumen. This is the case of
PPA, but the nature of the reaction is ill understood. In an effort to shed light on this
reaction, and before PPA-modified bitumens are studied further, it is beneficial to better
know the raw materials. Consequently, we briefly review here the chemistry and the
Bitumen
Bitumen is a residue of the distillation of crude oil. Most often this is a two-step process
where atmospheric and vacuum distillations are combined, in which case straight-run
bitumen is produced. When the distillation residue is oxidized in an effort to change its
The characteristics and composition of bitumen depend in large part on the source of the
mother crude oil, for instance, Canada, Mexico, Saudi Arabia, Venezuela (14). The
maltenes and the asphaltenes (As), which are, respectively, soluble and insoluble in n-
heptane. The maltenes can be fractionated further into saturates (S), aromatics (A) and
resins (R) (15, 16). The SARAs terminology can be confusing, however, because the
aromatics fraction (A) most often contains little conjugated ring structures (14). Table 1
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
3
[Table 1]
The molecular weight of the SARAs increase as S<A<R<As between 300 and 1000
Daltons (17, 18). Aromatic nuclei commonly have three to five condensed aromatic
rings (19). The bitumen molecules can thus be fairly large, with alkanes and pending
alkyl chains on aromatic nuclei providing for entanglements and viscoelastic properties.
repeat units. Bitumen can be regarded as an oligomer with about 10 repeat units, with
each repeat unit different from the next, and where the molecular weight of the repeat
The SARAs fractions also increase in aromaticity and heteroatomic content in the order
S<A<R<As (14). In bitumen, sulfur, oxygen and nitrogen can respectively attain about
8.5%, 1.2% and 1.5% by mass (21). Typical bitumen functional groups are shown in
Figure 1.
[Figure 1]
The miscibility of the SARAs fractions and the dispersion of the various functional
groups in bitumen are of great interest because they govern its chemical and physical
model, which states that asphaltenes are stabilized by the resins in a matrix of mixed
saturates and aromatics (22). A more recent model addresses the dispersion of the
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
4
neutral and amphoteric molecules, where adjacent acidic and basic functions interact to
Notwithstanding the success of the colloidal and the amphoteric models, both are based
view of bitumen in its solid state, by neglecting for instance the existence of ordered
modulated differential scanning calorimetry, MDSC (20, 24), and atomic force
microscopy, AFM (25, 26). These methods show that bitumen can contain at least six
phases and that it is heterogenous on a 15 m scale. MDSC shows that it can have four
glass transition temperatures from distinct amorphous phases, along with endothermic
asphaltenes whose ordering is time dependent (27, 28). Given this complexity, it is not
surprising that bitumens of identical classes can have different chemical compositions as
illustrated in Table 2 (21) for bitumens with a 58-28 grade (29). For this reason, it is
difficult to predict the stability or the reactivity of an additive in a mixture with bitumen.
[Table 2]
Polyphosphoric acid
The basic compounds for the production of polyphosphoric acid (PPA) are phosphorus
pentoxide (P2O5) and phosphoric acid (H3PO4), as shown in Figure 2. Phosphorus is first
oxidized to phosphorus pentoxide, which crystallizes as P4O10. Upon its reaction with
water, phosphoric acid is produced. This route to H3PO4 is known as the dry process,
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
5
which is used to provide high purity material (30, 31). A cheaper wet process provides
H3PO4 from the reaction of sulphuric acid on ground apatite phosphate rock,
[Figure 2]
PPA is an oligomer of H3PO4. High purity material is produced either from the
Figure 3 illustrates the equilibria for these reactions, which produce different chains
lengths and distributions. The dehydration method tends to produce short chains,
whereas the dispersion method usually produces chains with more than 10 repeat units
(32).
[Figure 3]
PPA is available in various grades, the naming of which can be confusing as the
percentage can exceed 100% (Table 3). One hundred percent phosphoric acid contains
72.4% P2O5 as calculated from the formula weight ratio P2O5/H3PO4. Similarly,
pyrophosphoric acid (H4P2O7) contains 79.8% P2O5 as calculated from the ratio
P2O5/H4P2O7. The ratio of these P2O5 contents provides a relative phosphoric acid
content, which for pyrophosphoric acid is 79.8%/72.4% = 110%. Other examples are
provided in Table 3.
The production of PPA provides a distribution of chain lengths, where the number of
repeat units in the PPA chain, n in Figure 3, varies from one chain to the next. Jameson
(32) characterized this distribution and found that 100% phosphoric acid is a mixture of
H3PO4 (orthophosphoric acid) with about 10% dimer (pyrophosphoric acid) by weight.
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
6
Figure 4 shows the distribution of chain lengths for three common commercial grades
used to modify bitumen. The 105% PA grade contains for the most part short monomeric
and dimeric segments, ortho and pyro phosphoric acids. In contrast, the 110% grade has
the same dimeric content, but little monomer, converted to segments with n > 3. In the
higher 114% grade, little monomer is left. They have all been converted to chains with 2
to 14 units. This increase in chain length leads to chain entanglements and explains the
[Table 3]
[Figure 4]
Koebner and Robinson (34) pioneered the use of PPA as a reagent in organic synthesis
when they produced a steroid skeleton after the cyclisation of a carboxylic acid. In the
seventy years since then, PPA has been found to be an effective reagent and solvent for
numerous synthetic applications, as detailed in several reviews (35, 36, 37), including
[Figure 5]
All phosphoric acids are acidic without being oxidizing, in contrast to mineral acids like
nitric acid (31). In water, the dissociation of the phosphoric acid and the release of the
protons follow the equilibria shown in Figure 6. Orthophosphoric acid has only one
strongly ionizing proton, with a pK1 of 2.1. The second proton, with a pK of 7.2, is not
more acidic than those of water. As the phosphoric acid chain length increases, however,
the acidity increases. The dimeric pyrophosphoric acid has two acidic hydrogens and the
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
7
trimeric triphosphoric acid has three (31). This increased acidity must be related to the
ability of the longer chains to stabilize multiple negative charges by tautomerization and
delocalization as shown in Figure 7 for the dimer. The longer the PPA chain, the greater
its acidity as each repeat unit can release a proton and stabilize the charge by resonance.
On a weight basis, however, the acidity of PPA is equal to that of H3PO4, which also
releases one proton per phosphorus atom. Moreover, upon dissolution of PPA in water,
the equilibrium shown in Figure 3a is shifted to the left so that PPA reverts back to
H3PO4. On an equal weight basis, the acidity of PPA in water is thus independent of
chain length.
[Figure 6]
[Figure 7]
Despite tabulated dissociation constants and the known acidic nature of PPA, its
possibly because the anion PPA, e.g. H2PO4, is amphoteric. Its dual acidic and basic
character is shown by the multiple equilibria in Figure 6. The action of PPA on alcohols
is a good example of its amphoteric activity, as the PPA- anion adds to alcohols to
PPA is also blended and reacted with bitumen (42). With the many functional groups in
bitumen, however, the exact reaction between PPA and bitumen can only be inferred.
Giavarini et al. (43) alluded to a reaction of PPA with asphaltenes, and Orange et al.
showed that it can occur by phosphorylation (44). Baumgardner et al. (45) concluded
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
8
It is noteworthy that PPA may be a very weak acid when mixed with bitumen. For PPA
to dissociate into PPA and H+, the medium must be of sufficiently high dielectric
constant (). Water is very polar. It has the highest dielectric constant of all solvents,
sphere can stabilize the charges of dissociated anions and cations (48). This stabilization
is gradually lost when water protons are replaced with non-polar alkyl groups (49). The
reduced potential for charge stabilization is shown, for example, by the reduced dielectric
constant for ethanol and ether in Table 4. Below a dielectric constant of 15, it is
generally considered that charge stabilisation is not possible (48). Consequently, in non-
polar bitumen ( = 3), PPA is unlikely to dissociate to its charged moieties, PPA and H+.
Any dissociation of PPA and reaction with bitumen would have to be localized to
bitumen enclaves with high dielectric constant, the existence of which is speculative, but
not incompatible with the grouping of several amphoteric groups (23), and nanodomains
(26).
[Table 4]
react with PPA and establish the level of PPA required for a given application. This is in
great part because the mechanism of PPA action on bitumen is unknown. To better
understand their reaction, or lack of, the characteristics of PPA and bitumen were briefly
reviewed. PPA has a high dielectric constant whereas that of bitumen is low, which
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
9
renders the dissociation of PPA into its acidic and basic moieties ineffective. PPA is thus
a very weak acid in bitumen. It can thus be postulated that PPA can only dissociate and
react with bitumen in enclaves of high dielectric constants formed from the aggregation
Acknowledgements
JFM thanks Dr Michael Falkiewicz for comments on the manuscript, and ICL
Performance Products LP and Paragon Technical Services, inc. for financial support.
References
(1) Anonymous, Asphalt Handbook, The Asphalt Institute, Manual Series No. 4 (MS-
4), Lexington, 1989.
(2) Kraus, G. Rubber Chem. Technol. 1982, 55, 1389-1402.
(3) Polacco, G.; Muscente, A. ; Biondi, D.; Santini. S. Effect of composition on the
properties of SEBS modified asphalts. European Polym. J. 2006, 42, 1113-121.
(4) Jew, P.; Shimizu, J.A.; Svazic. M.; Woodhams, R. T. Polyethylene-modified
bitumen for paving applications. J. Appl. Polym. Sci. 1986, 31, 2685-2704.
(5) Giavarini, C.; DeFilippis, P.; Santarelli, M. L.; Scarsella M. Production of stable
polypropylene-modified bitumens. Fuel 1996, 75, 681-686.
(6) Morrison, G. R.; Lee, J. K.; Hesp, S. A. M. Chlorinated polyolefins for asphalt
binder modification. J. Appl. Polym. Sci. 1994, 54, 231-240.
(7) Airey, G. D. Rheological evaluation of ethylene vinyl acetate polymer modified
bitumens. Const. Building Mat. 2003, 16, 473-487.
(8) Lee, Y. J.; France, L. M.; Hawley, M. C. Characterization of asphalt binders
mixed with epoxy terminated ethylene terpolymer. Proc. Polym. Mat. Sci. Eng.
1997, 76, 397-398.
(9) Polacco, G.; Stastna, J.; Biondi, D.; Antonelli, F.; Vlachovicova, Z.; Zanzotto, L.
Rheology of asphalts modified with glycidylmethacrylate functionalised
polymers. J. Colloid Interface Sci. 2004, 280, 366-373.
(10) Petrossi, U.; Bocca, P. L.; Pacor P. Reactions and technological properties of
sulfur-treated asphalt. Ind. Eng. Chem. Prod. Res. Develop., 1972, 11, 214-219.
(11) Fritschy, G.; Papirer, E.; Chambu, C. Sulfur modified bitumen: A new binder.
Rheol. Acta 1981, 20, 78- 84.
(12) Giavarini, C.; Mastrofini, D.; Scarsella, M. Macrostructure and rheological
properties of chemically modified residues and bitumens. Energy Fuels 2000, 14,
495-502.
(13) Anonymous, The Petroleum Handbook. Elsevier, New York, 6th ed., 1983.
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
10
(14) J.G. Speight, The Chemistry and Technology of Petroleum, 3rd ed., Marcel
Dekker, New York, 1999.
(15) Masson, J-F.; Price, T.; Collins, P. Dynamics of bitumen fractions by thin-layer
chromatography/flame ionization detection. Energy Fuels 2001, 15, 955-960.
(16) Raki, L.; Masson, J-F.; Collins, P. Rapid bulk fractionation of maltenes into
saturates, aromatics, and resins by flash chromatography. Energy Fuels 2000, 14,
160-163.
(17) Peramanu, S.; Pruden, B.B.; Rahimi, P. Molecular weight and specific gravity
distributions for Athabasca and Cold Lake bitumens and their saturate, aromatic,
resin, and asphaltene fractions. Ind. Eng. Chem., Res. 1999, 38, 3121-3130.
(18) Groenzin, H.; Mullins, O.C. Asphaltene molecular size and structure. J. Phys.
Chem. A 1999, 103, 11237-11245.
(19) Michon, L.; Martin, D.; Planche, J.-P.; Hanquet, B. Estimation of
average structural parameters of bitumens by 13C nuclear magnetic resonance
spectroscopy. Fuel, 1997, 76, 9-15.
(20) Masson, J-F.; Polomark, G. Bitumen microstructure by modulated differential
scanning calorimetry. Thermochim. Acta 2001, 374, 105-114. Erratum in 2004,
413, 273.
(21) Jones IV, D. SHRP Materials Reference Library for Asphalt Cements: A Concise
Data Compilation. Report SHRP-A-645, Strategic Highway Research Program,
National Research Council, Washington DC, 1993.
(22) Pfeiffer, J.P.H.; Saal, R.N.J. Asphaltic bitumen as colloid system. J. Phys. Chem.
1940, 44, 139149.
(23) Jones IV, D.R., SHRP Asphalt Research Program, Technical Memorandum #4,
1992, Center for Transportation Research, University of Texas, Austin, Texas.
(24) Masson, J-F.; Bundalo-Perc, S. Calculation of smoothing factors for the
comparison of dsc results. J. Therm. Anal. Calorim. 2007, 90, 639-643.
(25) Masson, J-F.; Leblond, V.; Margeson, J. Bitumen morphologies by phase-
detection atomic force microscopy. J. Microsc. 2006, 221, 17-29.
(26) Masson, J-F.; Leblond, V.; Margeson, J.; Bundalo-Perc, S. Low-temperature
bitumen stiffness and viscous paraffinic nano- and micro-domains by cryogenic
AFM and PDM. J. Microsc. 2007, 227, 191-202.
(27) Masson, J-F.; Polomark, G.; Collins, P. Time-dependent microstructure of
bitumen and its fractions by modulated differential scanning calorimetry. Energy
Fuels 2002, 16, 470-476.
(28) Masson, J-F.; Collins, P.; Polomark, G. Steric hardening and the ordering of
asphaltenes in bitumen. Energy Fuels 2005, 19, 120-122.
(29) Anonymous, ASTM D6373, Standard Specification for Performance Graded
Asphalt Binder.
(30) Averbuch-Pouchot, M.T.; Durif, A. Topics in Phosphate Chemistry, Chapter 3,
World Scientific, New Jersey, 1996.
(31) Corbridge, D. E. C. Phosphorus: An Outline of its Chemistry, Biochemistry and
Technology, Elsevier, New York, 5th ed., 1995.
(32) Jameson, R. F. The Composition of the Strong Phosphoric Acid. J. Chem.
Soc. 1959, 752-759.
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
11
(33) Platonov, V. A. Properties of polyphosphoric acid, Fibre Chem. 2000, 32, 325-
329.
(34) Koebner, A., and Robinson, R., Experiments on the synthesis of substances
related to the sterols. Part XXII. Synthesis of X-norequilenin methyl ether. J.
Chem. Soc. 1938, 1994-1997.
(35) Popp, F. D., and McEwen, W. E., Polyphosphoric acid as a reagent in organic
chemistry. Chem. Rev. 1959, 58, 321-401.
(36) Chebuliez, E. Organic Derivatives of Phosphoric Acid, Chap. 15 in Organic
Phosphorus Compounds, Kosolapoff, G. M.; Maier, L. Ed. Wiley-Interscience,
New York, 1973.
(37) Rowlands, D. A., Polyphosphoric acid (PPA), Chap. 3 in Synthetic Reagents Vol.
6, J. S. Pizey Ed., Ellis Horwood Publishers, Chichester, 1985.
(38) Chebuliez, E.; Weniger, H. Phosphorylations par les acides polyphosphoriques.
Helv. Chim. Acta 1946, 29, 2006-2017.
(39) Dev, S.; Rai, C. J. Organic reactions with polyphosphoric acid, part V.
Intramolecular acylation with lactones: cyclopentenones from -lactones. J.
Indian Chem. Soc. 1957, 34, 266-274.
(40) Stephenson, E. F. M. 3, 4-Dihydro-4-phenyl-carbostyril and -isocarbostyril and
some of their derivatives. J. Chem. Soc. 1967, 2557-2558.
(41) Kametani, T.; Nemoto, H. Studies on the syntheses of heterocyclic compounds
CDXVII Syntheses of 1,2-benzoxazepine, oxindole and furanoquinolone
derivatives by cyclization of hydroxamic acid with polyphosphoric acid. Chem.
Pharm. Bull. 1971, 19(7), 1325-1328.
(42) Alexander, S. H. Method of treating asphalt, US Patent 3,751,278, 1973.
(43) Giavarini, C.; Mastrofini, D.; Scarsella, M. Macrostructure and rheological
properties of chemically modified residues and bitumens, Energy Fuels 2000, 14,
495-502.
(44) Orange, G.; Dupuis, D.; Martin, J. V.; Farcas, F.; Such, C.; Marcant, B. Chemical
modification of bitumen through polyphosphoric acid : properties-microstructure
relationship, 3rd Euraphalt and Eurobitume Congress, Vienna 2004, Paper 334,
book 1, 733-745.
(45) Baumgardner, G. L.; Masson, J-F.; Hardee, J. R.; Menapace, A. M.; Williams, A.
G. Polyphosphoric acid modified asphalt: proposed mechanisms. Proc. Assoc.
Asphalt Paving Technologists 2006, 74, 283-305.
(46) Weast, R. C.and Astle, M. J. Eds, Handbook of Chemistry and Physics, CRC
Press, Boca Raton, 63rd edition, 1982, p. E50-E54.
(47) Munson, R. A., Dielectric constant of phosphoric acid. J. Chem. Phys 1964, 40,
2044-2046
(48) Lowry , T. H.; Richardson, K. S. Mechanisms and Theory in Organic Chemistry,
Harper and Row, New York, 2nd ed., 1981.
(49) Sykes, P. A Guidebook to Mechanism in Organic Chemistry, Longman, New
York, 5th edition, 1986, p. 374.
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
12
Captions
Figure 3. Production of PPA from the dehydration (a) and dispersion (b) methods. n is
an integer.
Figure 6. Dissociation of orthophosphoric acid and its constants. pK values are from
(30).
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
13
Fraction Composition
Saturates n- and iso-alkanes
Aromatics Alkylated cyclopentanes and cyclohexanes
Resins Alkylated and cycloalkylated aromatic rings
Asphaltenes Alkylated condensed aromatic rings
* From reference 14.
Name Structure
Water HOH 79
Phosphoric acids HOP(O)(OH)OH 61*
Ethanol HOCH2CH3 24
Ethyl ether CH3CH2OCH3CH2 4
Bitumen Hydrocarbon mixture 3
Benzene C6H6 2
Hexane C6H8 2
* From (48)
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
14
N O O
R O
H3C R
Ketones
S R
R Alkanes R Pyridines R R
Esters
Aromatic sulfides H OH R
N O
Alkyl- H3C S R
aromatics
R Sulfides R
Indoles R
S Phenols
O Ethers
R
R R
R
N O
Thiophenes H
Benzofurans
Quinolones
O
P
P4 + 5 O2 2 P2O5 (i.e., P4O10) O O
O O
O P P O
P
2 P2O5 + 6 H2O 4 H3PO4 (or 2 P2O5 3H2O) O O
O P4O 10
(a) O O
- (n - 1) H2O
n H3PO4 HO P O P O H
+ (n - 1) H2O OH OH n
(b) O
n P 2O 5
+ n H3PO4 HO P O H
3n
OH
Figure 3. Production of PPA from the dehydration (a) and dispersion (b) methods. n is
an integer.
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640
15
60.00
50.00 105%
Percent composition
110%
40.00 114%
30.00
20.00
10.00
0.00
1 3 5 7 9 11 13 15
Number of repeat units in PPA chain
OH OPPA Ph Ph
N O N O
H H
O
OEt O
O OEt
O O
N N O
OH H
Figure 5. Selected examples of synthetic applications of the effect of PPA on a starting
material.
Figure 6. Dissociation of orthophosphoric acid and its constants. pK values are from
(30).
- -
O O O O O O
H+
- -
HO P O P O HO P O P O HO P O P O
- + -
OH O H O OH O OH
Published in Energy & Fuels, Vol. 22, No. 4, 2008, pp. 2637-2640